KR20110042219A - Method for producing (meth)acrylosilanes - Google Patents

Abstract

The present invention starts from haloalkylsilane (S1) of the following general formula (2) and salt (S2) of unsaturated organic carboxylic acid of the following general formula (3) to produce silane (S) of the following general formula (1) As one or more components (L) having a boiling point lower than that of haloalkylsilane (S1), before or during the reaction of component (S1) with component (S2), distillation from the reaction mixture, partial mixture or individual reactant components To at least partially remove by means of:
(R ^{1 ′} ) ₂ C═C (R ¹ ) C (O) O— (R ² ) —Si (R ³ ) _z (OR ⁴ ) _3-z (1)
X- (R ² ) -Si (R ³ ) _z (OR ⁴ ) _3-z (2)
^{M w + [(R 1 '} ) 2 C = C (R 1) C (O) O -] w (3)
Wherein R ¹ , R ^{1 ′} , R ² , R ³ , R ⁴ , X, M ^{w +} , w and z have the meanings given in claim 1.

Description

Production method of (meth) acrylosilane {METHOD FOR PRODUCING (METH) ACRYLOSILANES}

The present invention relates to a process for preparing acrylosilanes and methacrylosilanes with fast reaction rates and high space-time yields.

Acrylosilanes and methacrylosilanes are, for example, sizing agents for glass fibers or in the manufacture of artificial marble, as adhesion promoters between inorganic and organic materials, or as crosslinking agents of organic polymers, for example paints, or It is used abundantly in the process of a filler.

Various methods are known for the preparation of such compounds. For example, DE # 2851456 or DE # 3832621 describes hydrosilylation using a noble metal catalyst in which a Si-H-containing compound is added and reacted with allyl (meth) acrylate. However, a disadvantage of these methods is the fact that in some cases a highly toxic alkoxysilane, such as for example trimethoxysilane, must be used, or an additional alcohol decomposition step is required if the corresponding chlorosilane, for example trichlorosilane, is used. to be. The latter is very undesirable, in particular due to the accompanying additional temperature load on (meth) acrylosilanes which have a tendency to polymerize. Moreover, according to this synthetic route, only the (meth) acrylosilane whose spacer between a silyl group and a (meth) acryl group has 3 or more carbon atoms can be manufactured. Particularly useful α- (meth) acryloyloxymethylalkoxysilanes cannot be obtained via this route due to the high reactivity in hydrolysis.

Thus, a more preferred and more common method of preparation is the process of preparing (meth) acrylosilanes by reaction of chloroalkylsilanes with alkali metal (meth) acrylates. To promote heterogeneous reactions, the reaction mixture is often mixed with a phase transfer catalyst. Methods of this type are described, for example, in EP # 0437653, EP # 1249454 or WO # 2007/063011.

However, the reaction rate of such a heterogeneous reaction is generally only moderate when the phase transfer catalyst is added. In other words, several hours of reaction time and a high reaction temperature of generally 70 ° C. to 120 ° C. are required to achieve near complete conversion.

This is a problem as long as the reaction product is sensitive to polymerization, in particular free radical polymerization. Since the polymerization of (meth) acrylate is a high exothermic reaction and its rate increases rapidly with increasing temperature, the risk of "runaway" polymerization is a safety risk that must be taken very seriously. In addition, polymer deposits of only a small proportion of the product can also lead to reduced yields and are difficult to remove (possibly only during distillation purification in which the formed polymer accumulates in the distillation bottom product) and can disrupt the manufacturing process sharply. May result in the formation of.

Free radical polymerization can be inhibited through the addition of free radical scavengers of the type described in many patents, for example EP'0'520'477. However, the effectiveness of such means is limited in terms of time, since free radical scavengers are consumed when expressing the effect.

In addition, it is an object to limit the amount of free radical scavenger used to a minimum. The reason is not only that this material is expensive, but also in particular due to the fact that even free radical scavengers and their decomposition products eventually become impurities, and thus undesirable properties may be expressed. For example, many stabilizers and the free radical scavengers described in EP '0'520 477 cause discoloration phenomena, for example. In turn, these materials affect the polymerization behavior even when the (meth) acrylosilanes must finally polymerize or copolymerize as intended. Such effects that may affect the properties of the polymer end product (eg, average chain length or chain length distribution) are generally undesirable.

Therefore, a synthetic method is preferred in which the reaction proceeds at the lowest possible temperature at the shortest possible time. This is even more so because the (meth) acrylosilanes are exposed to heat load not only in their synthesis but also in the purification process (usually distillation purification). Therefore, the overall load should be limited to the absolute unavoidable minimum level.

Therefore, it was an object of the present invention to improve the conventional process for preparing acrylosilanes or methacrylosilanes, so that the product can be produced in consistent quality but at lower temperatures and / or shorter reaction times.

The present invention starts from haloalkylsilane (S1) of the following general formula (2) and salt (S2) of unsaturated organic carboxylic acid of the following general formula (3) to produce silane (S) of the following general formula (1) As one or more components (L) having a boiling point lower than that of haloalkylsilane (S1), before or during the reaction of component (S1) with component (S2), distillation from the reaction mixture, partial mixture or individual reactant components It provides a method of preparation, which is at least partially removed by:

(R ^{1 ′} ) ₂ C═C (R ¹ ) C (O) O— (R ² ) —Si (R ³ ) _z (OR ⁴ ) _3-z (1)

X- (R ² ) -Si (R ³ ) _z (OR ⁴ ) _3-z (2)

^{M w + [(R 1 '} ) 2 C = C (R 1) C (O) O -] w (3)

(Wherein

R ¹ and R ^{1 ′} are each independently a hydrogen atom or a straight or branched chain hydrocarbon radical having 1 to 10 carbon atoms,

R ² is a straight or branched chain hydrocarbon radical of 1 to 40 carbon atoms, which may include one or more heteroatoms selected from nitrogen, oxygen, sulfur or phosphorus elements,

R ³ and R ⁴ are each independently a straight or branched chain hydrocarbon radical having 1 to 10 carbon atoms,

X is a halogen atom,

M ^{w +} is an alkali metal or alkaline earth metal ion,

^W corresponding to the valence of M ^{w +} may have a value of 1 or 2,

z may have a value of 0, 1 or 2.

The present invention is based on the surprising discovery that by removing distillation of the low boiling point component (L) from the reaction mixture, it is possible to significantly promote the reaction rate of the component (S1) and the component (S2). This increases the space-time yield.

In general formulas (1) to (3), R ¹ and R ^{1 ′} are preferably hydrogen or an alkyl radical having 1 to 3 carbon atoms, more specifically CH ₃ ; R ² is preferably an alkyl radical of 1 to 6 carbon atoms, more specifically a CH ₂ or (CH ₂ ) ₃ group; R ³ is preferably a CH ₃ or ethyl radical; R ⁴ is preferably a methyl, ethyl, propyl or isopropyl radical, with methyl and ethyl radicals being particularly preferred. X is preferably chlorine or bromine, more preferably chlorine. M ^{w +} is preferably an alkali metal ion selected from Li, Na, K, Rb and Cs ions, with sodium ions and especially potassium ions being particularly preferred.

Particularly preferably the process of the invention is used to prepare silanes (S) having methacryloyloxy or acryloyloxy functional groups.

Component (L) which is removed by distillation from the reaction mixture before or during the reaction of component (S1) with component (S2) and which has a boiling point lower than that of haloalkylsilane (S1) is preferably alcohol, water and / or trace (Meth) acrylic acid. Alcohols, more particularly alcohols (A) of the general formula (4):

R ⁴ OH (4)

Wherein R ⁴ has the same definition as described for General Formulas (2) and (3). Alcohol (A) of formula (4) may be introduced into the reaction mixture as impurities of both silane (S1) and salt (S2). It is also subject to transesterification in which the OR ⁴ groups on the silane functional groups of silane (S) or (S1) are replaced by other protic impurities (eg water, (meth) acrylic acid or other alcohols) present in the salt (S2). It may be formed by.

Since the (meth) acrylic acid salt (S2) generally contains a small amount of protic impurities, more specifically (meth) acrylic acid, water and / or alcohol, it is mentioned above on the silyl group of silane (S) or (S1). The substitution reaction thus indicated generally means that a certain amount of alcohol (A) is present in the reaction mixture in the reaction modes described in the prior art, the value of which can be reduced through the removal of the low boiling point component (L) according to the invention. This surprisingly leads to the effects of the invention mentioned above.

In the reaction of the component (S1) and the component (S2), preferably, at least one phase transfer catalyst (P) and at least one stabilizer (St) are used. Examples of phase transfer catalysts (P) include compounds described in EP # 0437653, EP # 1249454 or WO # 2007/063011, more specifically tetraorganoammonium salts or tetraorganophosphonium salts, for example tetrabutylphosphonium chloride or bromide, butyltree Butylphosphonium chloride or bromide, methyltributylphosphonium chloride or bromide and methyltriphenylphosphonium chloride. Tertiary phosphines of the general formula (5) below can also be used as phase transfer catalyst (P).

R ⁵ ₃ P (5)

Wherein R ⁵ is an optionally substituted monovalent hydrocarbon radical of 1 to 20 carbon atoms, which in each case may be the same or different and may be interrupted by an oxygen atom and / or a nitrogen atom.

Preferred phosphines are, for example, tributylphosphine, trioctylphosphine or triphenylphosphine. The phase transfer catalyst (P) is preferably used in an amount of 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the amount of silane (S1) used in each case.

Stabilizers (St) are commercially available compounds of the type described, for example, in EP 0 520 477. These stabilizers include aromatic amines, quinones, hydroquinones, steric hindrance phenols or stable free radicals such as phenothiazines, hydroquinones, hydroquinone monomethyl ethers, N, N'-diphenyl-p-phenylenediamines, 2, 6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4 (N, N-dimethylamino) methylphenol, 2,2, 6,6-tetramethylpiperidyl N-oxide or 3,5-di-tert-butyl-4-hydroxytoluene. Stabilizer (St) is used in an amount of 0.01 to 1% by weight, more preferably 0.05 to 0.4% by weight, based on the amount of silane (S1) used in each case.

Oxygen may act as an auxiliary stabilizer. For this reason, the reaction of the present invention can be carried out in lean air, that is, in oxygen containing 0.1 to 2% oxygen.

Phase transfer catalyst (P) and stabilizer (St) may optionally be added as a solution in one or more solvents (L1). Any solvent may be used as the solvent (L1), but a conventional volatile solvent is preferably used, and examples thereof include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, alcohols such as methanol , Ethanol, propanol and butanol, ethers such as THF, dioxane, diethyl ether and methyl tert-butyl ether, aromatic compounds such as toluene and xylene, or alkanes such as pentane, hexane, cyclohexane and heptane.

In the method of the present invention, it is preferable to remove the solvent (L1) together with the volatile component (L).

In one preferred embodiment of the process of the invention for preparing the silane (S) of formula (1), the process is

First feeding a haloalkylsilane (S1) of formula (2),

At least partially removing by distillation at least one component (L) having a boiling point lower than that of haloalkylsilane (S1),

Adding a salt of unsaturated organic carboxylic acid of formula (3) (S2)

It is characterized by.

These process steps are preferably performed in the order described.

In a further process step, it is also preferred to add at least one phase transfer catalyst (P) and / or at least one stabilizer (St), or a solution of at least one of these components in solvent (L1). This addition can be carried out before, during or after the initial feed of silane (S1). It is also possible to premix the components (P), (St) and / or (L1) with halosilanes (S1) and feed them together.

Particular preference is given to adding a solution of at least one phase transfer catalyst (P) and optionally at least one stabilizer (St) in solvent (L1) before (part) removal of the more volatile component (s) (L). Thus, in this removal process step, the solvent (s) L1 are also completely or at least partially removed.

In addition, the reaction mixture may comprise one or more solvents. However, it is preferred to carry out the reaction without solvent.

In carrying out the process of the method of the present invention, the low boiling point component (L) is preferably removed by supplying some or all of the reaction components to the reaction vessel and lowering the pressure to the extent that the mixture is boiling. Thereafter, preferably, 0.1 to 5% by weight of the total reaction mixture is removed by distillation.

In one example of the preferred process, the silane of formula (1) is already included and optionally already contains a phase transfer catalyst (P) and / or stabilizer (St) but no salt (S2) yet. The low boiling point component is removed from the mixture. In another preferred variant, the low boiling point component (L) is removed after all or part of the (meth) acrylate salt (S2) is also added. Particular preference is given to carrying out the distillation step to remove the low boiling point component (s) (L) before or at the beginning of the reaction and at least one further distillation step during the reaction. This is because during the reaction, a small amount of alcohol (A) is newly formed due to the abovementioned substitution on the silyl groups of silane (S) and / or (S1), for example as the salt (S2) is dissolved. Particularly suitable when the traces of water from salt (S2) result in the hydrolysis reaction of silane (S) or (S1). This trace of alcohol is then removed by an additional distillation step.

The amount of free alcohol (A) of formula (4) in components (S1) and (S2) is preferably in each case preferably 4% by weight or less, more specifically 2% by weight or less, based on the total reaction mixture, Particular preference is given to values up to 1.5% by weight or up to 1% by weight.

In one of the preferred embodiments, the distillation off of the low boiling point component (L) is carried out at the reaction temperature and / or during the warming step and is only controlled by the pressure and / or reflux ratio of the cooler. This has the advantage that there is no time loss due to long heating and cooling steps.

The temperature during the distillation of the volatile component (L) and / or during the reaction of the haloalkylsilane (S1) of the general formula (2) and the salt (S2) of the unsaturated organic carboxylic acid of the general formula (3) is preferably 60 ° C. or higher. More preferably, it is 70 degreeC or more, Preferably it is 150 degrees C or less, More preferably, it is 120 degrees C or less. Any residues of halogen salts formed as by-products and optionally (meth) acrylic acid salts with anions of the general formula (4) are preferably removed by filtration. The product is then purified, preferably by distillation, with one or more purification steps carried out. It is preferable to first separate the low boiling point impurities by distillation. This is preferably carried out under reduced pressure at a temperature of at least 20 ° C, more preferably at least 40 ° C, preferably at most 120 ° C, more preferably at most 80 ° C.

Thereafter, if necessary, the silane (S) of general formula (1) itself is distilled, and this distillation step is also preferably performed under reduced pressure, so that the liquidus temperature during distillation is 200 ° C or lower, preferably 150 ° C or lower. More preferably, it is 130 degrees C or less.

Examples of the unsaturated silicon compound (S) of the general formula (1) include acrylosilanes such as acryloyloxymethyltrimethoxysilane, acryloyloxymethyltriethoxysilane and acryloyloxymethyltriphenyl Oxysilane, acryloyloxymethyltriisopropoxysilane, acryloyloxymethyltris (2-methoxyethoxy) silane, acryloyloxymethyl (methyl) dimethoxysilane, acryloyloxymethyl (methyl) Diethoxysilane, acryloyloxymethyl (methyl) diphenyloxysilane, acryloyloxymethyl (methyl) diisopropoxysilane, acryloyloxymethyl (methyl) bis (2-methoxyethoxy) silane, Acryloyloxymethyl (dimethyl) methoxysilane, acryloyloxymethyl (dimethyl) ethoxysilane, acryloyloxymethyl (dimethyl) phenyloxysilane, acryloyloxymethyl (dimethyl) isopropoxysilane, acryl Royloxymethyl (dimethyl) (2-methoxyethoxy) silane, 3-acryloyloxy Lofiltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriphenyloxysilane, 3-acryloyloxypropyltriisopropoxysilane, 3-acryloyloxypropyl Tris (2-methoxyethoxy) silane, 3-acryloyloxypropyl (methyl) dimethoxysilane, 3-acryloyloxypropyl (methyl) diethoxysilane, 3-acryloyloxypropyl (methyl) di Phenyloxysilane, 3-acryloyloxypropyl (methyl) diisopropoxysilane, 3-acryloyloxypropyl (methyl) bis (2-methoxyethoxy) silane, 3-acryloyloxypropyl (dimethyl ) Methoxysilane, 3-acryloyloxypropyl (dimethyl) ethoxysilane, 3-acryloyloxypropyl (dimethyl) phenyloxysilane, 3-acryloyloxypropyl (dimethyl) isopropoxy silane, 3- Acryloyloxypropyl (dimethyl) (2-methoxyethoxy) silane or methacrylosilane, for example methacryloyloxy Methyl trimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltriphenyloxysilane, methacryloyloxymethyltriisopropoxysilane, methacryloyloxymethyltris (2- Methoxyethoxy) silane, methacryloyloxymethyl (methyl) dimethoxysilane, methacryloyloxymethyl (methyl) diethoxysilane, methacryloyloxymethyl (methyl) diphenyloxysilane, methacrylo Iloxymethyl (methyl) diisopropoxysilane, methacryloyloxymethyl (methyl) bis (2-methoxyethoxy) silane, methacryloyloxy methyl (dimethyl) methoxysilane, methacryloyloxy Methyl (dimethyl) ethoxysilane, methacryloyloxymethyl (dimethyl) phenyloxysilane, methacryloyloxymethyl (dimethyl) isopropoxysilane, methacryloyloxymethyl (dimethyl) (2-methoxy to Methoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyl Ethoxysilane, 3-methacryloyloxypropyltriphenyloxysilane, 3-methacryloyloxypropyltriisopropoxysilane, 3-methacryloyloxypropyltris (2-methoxyethoxy) silane, 3-methacryloyloxypropyl (methyl) dimethoxysilane, 3-methacryloyloxypropyl (methyl) diethoxysilane, 3-methacryloyloxypropyl (methyl) diphenyloxysilane, 3-methacryl Loyloxypropyl (methyl) diisopropoxysilane, 3-methacryloyloxypropyl (methyl) bis (2-methoxyethoxy) silane, 3-methacryloyloxypropyl (dimethyl) methoxysilane, 3-methacryloyloxypropyl (dimethyl) ethoxysilane, 3-methacryloyloxypropyl (dimethyl) phenyloxysilane, 3-methacryloyloxypropyl (dimethyl) isopropoxysilane, 3-methacryl Royloxypropyl (dimethyl) (2-methoxyethoxy) silane.

An example of especially preferable unsaturated organosilicon compound (S) of General formula (1) is a compound whose R <^2> is a methylene group. Such silanes are generally characterized by having particularly high reactivity with an especially high tendency for polymerization. Particularly preferred are acryloyloxymethyltrimethoxysilane, acryloyloxymethyltriethoxysilane, acryloyloxymethyl (methyl) dimethoxysilane, acryloyloxymethyl (methyl) diethoxysilane, acryloyl Oxymethyl (dimethyl) methoxysilane, acryloyloxymethyl (dimethyl) ethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyl ( Methyl) dimethoxysilane, methacryloyloxymethyl (methyl) diethoxysilane, methacryloyloxymethyl (dimethyl) methoxysilane and methacryloyloxymethyl (dimethyl) ethoxysilane.

All of the above signs of the above formulas have their definitions independently of one another in each case. In all formulas the silicon atom is tetravalent.

In the following examples and comparative examples, unless otherwise specified, all positive values and percentage values are expressed by weight, and all reactions are carried out at a pressure of 0.10 MPa (absolute pressure) and a temperature of 20 ° C. do.

Inventive Example 1:

Into a 500 ml flask equipped with a KPG stirrer, cooler and thermometer, 319.12 μg (1.50 μmol) of chloromethyltriethoxysilane was first added, followed by 8.85 μg of tetrabutylphosphonium chloride and 0.15 μg of phenothiazine. Add. This charge is heated to 110 ° C. in an oil bath and 195.6 g (1.575 mol) of potassium methacrylate is added. At the end of the addition, the pressure in the reaction vessel is lowered to 100 kmbar and the total boiling point of low boiling point component is removed by distillation. Thereafter, the pressure is raised to atmospheric pressure again. During distillation and throughout the subsequent reaction, the reaction temperature is kept constant at 108 ° C to 112 ° C. After 1 hour of total reaction time (including distillation at the start of the reaction), the conversion to methacryloyloxymethyltriethoxysilane, as measured by GC, is about 82 mmol%. After 2 hours the conversion is about 92 mol%. After 4 hours, the reaction is almost complete (ie, the amount of unreacted chloromethyltriethoxysilane is less than 0.5 mol%). In all samples, the ethanol content is 1.2-1.5 mmol% and tends to rise slightly during the reaction.

The potassium chloride formed is filtered and then the product is distilled off using a laboratory short-path evaporator. This gave a product of about 94% yield and about 98.5% purity.

Inventive Example 2:

Into a 500 ml flask equipped with a KPG stirrer, cooler and thermometer, 319.12 μg (1.50 μmol) of chloromethyltriethoxysilane was first added, followed by 8.85 μg of tetrabutylphosphonium chloride and 0.15 μg of phenothiazine. Add. This charge is heated to 110 ° C. in an oil bath and 195.6 g (1.575 mol) of potassium methacrylate is added. At the end of the addition, the pressure in the reaction vessel is lowered to 100 kmbar and the total boiling point components of about 14 g are removed by distillation. Thereafter, the pressure is raised to atmospheric pressure again. During distillation and throughout the subsequent reaction, the reaction temperature is kept constant at 108 ° C to 111 ° C. After 1 hour of total reaction time (including distillation at the start of the reaction), the conversion to methacryloyloxymethyltriethoxysilane, as measured by GC, is about 83 mmol%. Subsequently, as a further lowering of the pressure, about 6 g of distillate is further distilled off. After 2 hours, less than 0.2 mol% of reactant is present in the reaction mixture. After 1 hour the ethanol content in the primary sample is 1.3 mol% and after 2 hours the ethanol content in the secondary sample is 0.9 mol%.

Comparative Example 1:

The procedure of Example 1 is repeated except that the distillation step after the addition of potassium methacrylate is omitted. After 1 hour, the conversion measured by GC is about 40 mmol%. After 2 hours the conversion is about 59 mol%. Finally, after 4 hours, a conversion rate of about 81 mmol% is obtained. The ethanol content in all samples remained relatively constant at 2.0-2.1 mmol%.

Inventive Example 3:

Into a 500 ml flask equipped with a KPG stirrer, a cooler and a thermometer, 231.98 μg (1.50 μmol) of chloromethylmethyldimethoxysilane was first added, followed by 8.85 μg of tetrabutylphosphonium chloride and 0.15 μg of phenothiazine. Add. This charge is heated to 90 ° C. in an oil bath and 195.6 g (1.575 mol) of potassium methacrylate is added. At the end of the addition, the pressure in the reaction vessel is lowered to about 700 mbar and the total boiling point of about 7.8 g of the low boiling point component is removed. Thereafter, the pressure is raised to atmospheric pressure again. During the distillation and throughout the subsequent reaction, the reaction temperature is kept constant at 88 ° C to 90 ° C. After 1 hour of total reaction time (including distillation at the start of the reaction), the conversion to methacryloyloxymethylmethyldimethoxysilane, as measured by GC, is about 93 mol%. Subsequently, as the pressure is further lowered, about 4.1 g of distillate is further distilled off. After 2 hours, the conversion is 99 mol% and after 3 hours less than 0.2 mol% of reactant is present in the reaction mixture. After 1 hour the methanol content in the primary sample is 1.0 mol% and after 2 hours and 3 hours the methanol content in the secondary and tertiary samples is 0.8 mol%.

After the potassium chloride formed is filtered, the product is distilled off using a laboratory single evaporator. This yields a product of about 92% yield and about 98.2% purity.

Comparative Example 2:

The procedure of Example 2 was repeated except that the distillation step after addition of potassium methacrylate and after 1 hour of reaction time was omitted. After the reaction time of 1 hour, the conversion measured by GC is about 75 mmol mol%. After 2 hours, the conversion is about 85 mol%. Finally after 3 hours a conversion of about 93 mol% is obtained. After 4 hours, a satisfactory level of conversion of about 97% is obtained. The methanol content in all samples remained relatively constant at 1.6-1.7 mmol%.

[Effects of the Invention]

According to the present invention, acrylosilanes or methacrylosilanes can be produced in consistent quality at lower temperatures and / or shorter reaction times compared to conventional preparation methods.

Claims (11)

As a method of producing the silane (S) of the following general formula (1) starting from the haloalkylsilane (S1) of the following general formula (2), and the salt (S2) of the unsaturated organic carboxylic acid of the following general formula (3), A component At least in part by distilling from the reaction mixture, the partial mixture or the individual reactant components one or more components (L) having a boiling point lower than that of the haloalkylsilane (S1) before or during the reaction of (S1) with component (S2). Method to remove by:
(R ^{1 ′} ) ₂ C═C (R ¹ ) C (O) O— (R ² ) —Si (R ³ ) _z (OR ⁴ ) _3-z (1)
X- (R ² ) -Si (R ³ ) _z (OR ⁴ ) _3-z (2)
^{M w + [(R 1 '} ) 2 C = C (R 1) C (O) O -] w (3)
(Wherein
R ¹ and R ^{1 ′} are each independently a hydrogen atom or a straight or branched chain hydrocarbon radical having 1 to 10 carbon atoms,
R ² is a straight or branched chain hydrocarbon radical of 1 to 40 carbon atoms, which may include one or more heteroatoms selected from nitrogen, oxygen, sulfur or phosphorus elements,
R ³ and R ⁴ are each independently a straight or branched chain hydrocarbon radical having 1 to 10 carbon atoms,
X is a halogen atom,
M ^{w +} is an alkali metal or alkaline earth metal ion,
^W corresponding to the valence of M ^{w +} may have a value of 1 or 2,
z may have a value of 0, 1 or 2. The process according to claim 1, wherein R ¹ and R ^{1 '} are a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms. The process according to claim 1, wherein R ³ is preferably a CH ₃ or ethyl radical. The production process according to any one of claims 1 to 3, wherein X is chlorine. The process according to any one of claims 1 to 4, wherein component (L) comprises an alcohol (A) of the following general formula (4):
R ⁴ OH (4)
In the formula, R ⁴ has the same definition as described in claim 1 for general formulas (2) and (3). The process according to any one of claims 1 to 5, wherein at least one phase transfer catalyst (P) is present. The manufacturing method in any one of Claims 1-6 whose temperature during the distillation of a volatile component (L) is 60 degreeC-150 degreeC. The temperature in any one of Claims 1-7 in reaction of haloalkylsilane (S1) of General formula (2) and the salt (S2) of unsaturated organic carboxylic acid of General formula (3) is 60 degreeC-150 The manufacturing method which is ° C. The method of claim 1, wherein at least
First feeding a haloalkylsilane (S1) of formula (2),
At least partially removing by distillation at least one component (L) having a boiling point lower than that of haloalkylsilane (S1),
Adding a salt of unsaturated organic carboxylic acid of formula (3) (S2)
&Lt; / RTI &gt; 10. The process according to claim 9, wherein at least one phase transfer catalyst (P) and optionally at least one stable in at least one solvent (L1) before completely or partially removing the more volatile component (s) (L). A solution of the agent (St) is added and in the removal process step, the solvent (s) (L1) are also completely or at least partially removed. The method according to any one of claims 1 to 10, wherein, in the reaction of component (S1) with component (S2), the amount of free alcohol (A) of the following general formula (4) is 4 weights based on the total reaction mixture. Manufacturing method that is% or less:
R ⁴ OH (4)
Wherein R ⁴ has the same definition as described for General Formulas (2) and (3).